Carbamoyloxyimino-azolidines as insecticides

ABSTRACT

Compounds of the formula   WHEREIN Q is sulphur, sulphoxide, sulphone or oxygen; R1 and R2 which may be the same or different are hydrogen or alkyl containing up to four carbon atoms; R3 is hydrogen, alkyl containing up to eight carbon atoms, allyl, benzyl, dimethylamino, methyl-thiomethyl, ethoxycarbonylmethyl, or halosubstituted pyridyl; and either (i) X is a group of the formula:   where R4 and R5, which may be the same or different, are hydrogen, alkyl containing up to four carbon atoms, phenyl, chlorosubstituted phenyl, acetyl, chloromethyl, methoxymethyl, ethoxymethyl or ethylthiomethyl; and Y is oxygen, sulphur or alkylimino containing up to four carbon atoms; or (ii) Y is a group of the formula:   where R4 and R5, which may be the same or different, are hydrogen, alkyl containg up to four carbon atoms, phenyl, chlorosubstituted phenyl, acetyl, chloromethyl, methoxymethyl, ethoxymethyl or ethylthiomethyl; and X is oxygen, sulphur or alkylimino containing up to four carbon atoms; useful as pesticides.

United States Patent 1191 Punja 1 1 CARBAMOYLOXYIMINO-AZOLIDINES AS INSECTICIDES [75] Inventor: Nazim Punja, Wokingham, England [731 Assignee: Imperial Chemical Industries Limited, London, England [22] Filed: June 10, 1974 [21] App]. No.: 478,043

Related US. Application Data [621 Division of Scr. No. 250,119, May 4, 1972, Pat. No.

Primary Examinerlerome D. Goldberg Ass/slant ExaminerA1len J. Robinson Attorney, Agent, or FirmCushman, Darby & Cushman [57] ABSTRACT Compounds of the formula "R3 //Y X 1 1 July 29, 1975 wherein Q is sulphur, sulphoxide, sulphone or oxygen; R and R which may be the same or different are hydrogen or alkyl containing up to four carbon atoms; R is hydrogen, alkyl containing up to eight carbon atoms, allyl, benzyl, dimethylamino, methylthiomethyl, ethoxycarbonylmethyl, or halo-substituted pyridyl; and either (i) X is a group of the formula:

where R and R", which may be the same or different, are hydrogen, alkyl containing up to four carbon atoms, phenyl, chlorosubstituted phenyl, acetyl, chloromethyl, methoxymethyl, ethoxymethyl or ethylthiomethyl; and Y is oxygen, sulphur or alkylimino containing up to four carbon atoms; or (ii) Y is a group of the formula:

where R and R which may be the same or different, are hydrogen, alkyl containg up, to four carbon atoms, phenyl, chlorosubstituted phenyl, acetyl, ch1oromethyl, methoxymethyl, cthokymethyl or ethylthiomethyl; and X is oxygen, sulphur or alkylimino containing up to four carbon atoms useful as pesticides.

6 Claims, No Drawings Wherein Q is oxygen or sulphur, or the sulphoxide or sulphone group; R, R and R which may be the same or different, are hydrogen, or unsubstituted, or substi tuted, hydrocarbyl or heterocyclic radicals; and either (i) X is a group of formula:

where R and R which may be the same or different, are hydrogen, or unsubstituted, or substituted, hydrocarbyl radicals, or the acyl residues of carboxylic or sulphur-containing acids; and Y is oxygen, sulphur or the hydrocarbylimino radical; or (ii) Y is a group of formula:-

where R and R which may be the same or different, are hydrogen, or unsubstituted, or substituted, hydrocarbyl radicals, or the acyl residues of carboxylic or sulphur-containing acids; and X is oxygen, sulphur, or the hydrocarbylimino radical. In one aspect the invention also provides compounds of formula:-

F vi

wherein R, R and R are hydrogen atoms or unsubstituted, or substituted, hydrocarbyl groups; n has the value zero, one or two; and wherein either (i) X is a group of formula:-

where R and R are hydrogen or hydrocarbyl groups. and Y is oxygen or sulphur or the hydrocarbylimino group; or (ii) Y is a group of the formula:-

where R and R are hydrogen or hydrocarbyl groups, and X is oxygen or sulphur or the hydrocarbylimino group.

Preferred compounds are those provided by the invention of formula:-

R I. kg

wherein Q is oxygen, or sulphur, or the sulphoxide or sulphone group; R and R which may be the same or different are hydrogen or alkyl; R is hydrogen, alkyl, alkenyl, alkylthioalkyl, alkyl-substituted amino, aralkyl, ester-substituted alkyl, or a halo-substituted nitrogen-containing aromatic m'onocyclic heterocycle; and either (i) X is a group of formula:-

where R and R which may be the same or different, are hydrogen, alkyl, phenyl, halo-substituted phenyl, acyl, haloalkyl, alkoxyalkyl or alkylthioalkyl; and Y is oxygen, sulphur or alkylimino; or (ii) Y is a group of formula:-

where R and R which may be the same or different, are hydrogen, alkyl, phenyl, halosubstituted phenyl, acyl, haloalkyl, alkoxyalkyl or alkylthioalkyl; and X is oxygen, sulphur or alkylimino.

In a more preferred aspect the invention provides compounds of formula:

Wherein R and R which may be the same or different are hydrogen or alkyl; R is hydrogen, alkyl, alkenyl, alkylthioalkyl, alkyl-substituted amino, aralkyl, estersubstituted alkyl, or a halo-substituted nitrogencontaining aromatic monocyclic heterocycle; and R and R which may be the same or different, are hydrogen, alkyl, phenyl, halo-substituted phenyl, acyl, haloalkyl, alkoxyalkyl or alkylthioalkyl.

In a even yet more preferred aspect the invention provides compounds of formula:-

Wherein R and R which may be the same or different, are hydrogen, or alkyl containing up to four carbon atoms; R is hydrogen, alkyl containing up to eight carbon atoms, allyl, benzyl, dimethylamino, methylthiomethyl, ethoxycarbonylmethyl, or halo-substituted pyridyl; and R and R which may be the same or different, are hydrogen, methyl, phenyl, chlorosubstituted phenyl, acetyl, chloromethyl, methoxymethyl, ethoxymethyl or ethylthiomethyl.

Especially preferred compounds are those having the formula:-

Wherein R is alkyl containing up to four carbon atoms; R and R are hydrogen or alkyl containing up to four carbon atoms; R is hydrogen or methyl; and R is methyl.

Specific examples of compounds according to the formula:

are set out in Table I below, where the meanings of R, R R R and R are given together with a melting point (m.p.) each compound expressed in degrees centigrade.

TABLE I Compound No: R R R R R mp. C

1 H H CH CH CH,) CH, H 122 2 H H CH, CH, H 216 3 H H C H, CH, H 218 4 CH, CH, CH, CH, H l34.5 5 H H n-C,H, CH, H 126 6 H H nC,H,, CH, CH, 52 7 CH, CH, CH, CH, CH, 137 8 CH, CH, H CH, H 240 9 CH, H CH, CH, H 138 10 CH, CH, C,H, CH, H 107 I l H H CH, CH, CH, 168 I2 CH, CH, CH(CH,) CH, H 97 13 CH, CH, CH,sCH, CH, H 106 I4 CH, CH, H CH, COCH, 161 I5 CH, CH CH CH=CH CH, H 76 I6 CH CH(CH,) H CH, CH, H I7 C H, H CH, CH, H I05 18 CH, CH, CH, CH, H 98 19 CH(CH,) H CH, CH, H I20 20 C, C,H, H CH, H 162 21 CH,CH CH, H C CH, H 100 22 C,H, C,H, CH, CH, H 104 23 CH, CH, N(CH,) Ch, H I18 24 CH(CH,) H C,H, CH, H 91 25 2 nC,H, H CH, H I45 26 C- H, n-C, CH, CH, H Oil 27 CH, CH, CH, H H Suhlimes at 300 28 H H CH, CH; H

TABLE I Continued Compound No: R R R" R R mp. C 29' (l-1;, CH CH ,C,H,, CH, H 120 30 CH CH CH2CH(CH3)Q CH H 103 31 CH CH CH COOC H CH H 112 32 3 2 s 1; :1 n H 80 33 CH CH CH CH CH Cl l42 34 CH CH CH CH CH SC H 74 35 CH CH CH CH CH OCH l 16 36 CH CH; CH CH CH OC H 68 37 CH, CH, CH, Q H 143 c1 7 38 CH CH(CH H H CH H I30 39 CH(CH:x)-: H H CH H 120 40 C- H H H CH H 105 C] F 41 CH3 CH3 6 CH; H 210 42 CH CH CHgCOC(CH5 )3 CH H l64 in another aspect the invention provides compounds of formula:

Wherein R, R and R are alkyl groups containing up to four carbon atoms; R and R are hydrogen or alkyl containing up to four carbon atoms, and n has the value one 01' tWO.

5 /N- 3- ON Specific compounds according to the formula:-

are set out in Table 2 below, where the meanings of R, R, R, R and R are given, together with the value of n and a melting point for each compound.

In another aspect the invention provides compounds of formula:-

3 R Y R l o 30 i-li-0-N:

are set out in Table 3 below, where the meanings of Y, R, R, R, R and R are given together with a melting point for each compound.

TABLE 2 Compound No. R R R R R n m.p.C

43 CH CH CH CH H 2 118 43A CH CH CH CH H l & 2 Oil TABLE 3 Compound No. R R R" R R Y m.p.C

44 CH CH CH H CH S l47 4S CH CH CH CH CH S 218 46 CH CH CH NC H, Oil

In another aspect the invention provides compounds Wherein R, R and R are alkyl groups containing up to four carbon atoms; and R and R are hydrogen or alkyl groups containing up to four 'carbon atoms, A further specific compound of the present invention is that 1 having the formula:-

(Compound No. 47, mp. 135C) The invention compounds may be prepared by treating an oxime of formula:

Wherein R, R R and Q have any of the meanings as defined hereinbefore and either (i) A is a group N-OH and B is oxygen, sulphur or a hydrocarbylimino group, or (ii) B is a group N-Ol-l and is oxygen sulphur or a hydrocarbylimino group, with a carbamoylating 4 agent. Such agents include isocyanates, carbamoylhalides, and phosgene with ammonia or an amine.

Thus the invention provides a process for the preparation of compounds of the formula:

wherein R, R R and R have any of the meanings as R defined hereinbefore and wherein R" is hydrogen which ,5 comprises treating an oxime of formula:-

V i l with an isocya nate of formula:-

R -N=C=O The invention also provides a process for the preparation of a compound of the formula:-

now

wherein R, R R, R and R have any of the meanings as defined hereinbefore except that R and R cannot be hydrogen, which comprises treating an oxime of formula:-

HON:

with a carbamoylhalide of the formula:-

N- -Hai wherein Hal is a halogen atom, for example, a chlorine or bromine atom.

The invention also provides a process for the preparation of a compound of formula:-

9 wherein R, R R, R and R have any of the meanings as defined hereinbefore, which comprises treating an oxime of formula:-

HON with phosgene and then bringing the product of such treatment into reaction with an amine of formula R R NH.

Such carbamoylation reactions are as outlined above are conveniently carried out in the presence of a base. Suitable bases include tertiary amines, for example triethylamine, or dicthylaniline, aprotic nitrogen heterocycles for example pyridine or N-methylmorpholine, and alkali metal carbonates for example potassium carbonate. The reactions may also be carried out in the presence of a solvent or diluent, preferably a nonhydroxylic solvent, for example, chloroform, pyridine, aromatic hydrocarbons or petroleum ether.

Compounds of formula:

may also be prepared by the treatment of a compound 40 of formula:

with a halogen compound of formula R Hal, conveniently in the presence of a base, for example sodium hydride. Compounds of formula:-

wherein R, R R, R and R have any of the meanings as defined hereinbefore and n has the value one or two may be prepared by the oxidation of a compound of formula:-

R O R E TJ/ \N" ON with an oxidising agent, for example, hydrogen peroxide in the presence of an acid, for example acetic acid. Compounds of formula:-

may be prepared by any of the carbamoylation procedures outlined above from an oxime of formula:-

wherein R is an acyl groupmay be obtained by treating an invention compound of formula:-

with an acylating agent, for example an acyl halide.

lnvention compounds of formul:-

3 3 R Y R J ,JJ

9 HO /N b O N 1 5 3- -R R 1 wherein R is a chloromethyl group may be obtained by 10 The thiongs f f l treatment of a compound of formula:- 1

P.) R3 Q 0 with formaldehyde and hydrogen chloride. Such chlol romethylated compounds y be Subsequently reacted may be obtained by the well-known method of reacting with alcohols and thiols to yield invention compounds together a ccmpound f f l wherein R is alkoxyalkyl or alkylthioalkyl. r v

The oximes used as intermediates in the preparation 7 r. i v S of the invention compounds may be obtained by treat- I ment of the corresponding thiones with hydroxyl- 3 amines, thus for example a compound of formula:-

' 3 3 R (usually in the form of a metal or ammonium salt I thereof) with a haloacid of formula:- N or N Sj-- 1 R i Hal 0 Coca 2 Wherein R, R and R have any of themeanings as defined hereinbefore, may be treated with hydroxylamine where Ha] is a halogen atom.

to Yield an Oxime of formula." An alternative method of preparing the oximes of formula:-

R 3 L or i R no son I l s n o I '"i non. R a I 1 R Similarly a compound of formula:- a

particularly those wherein R is hydrogen atom, involves the treatment of an imine of formula:- I A v S a g N Where Y, R, R and R" have any of the meanings as defined hereinbefore, may be treated with hydroxylamine R to give the oxime of formula? with hydroxylamineI Such imines may be obtained by the reaction of a thiourea of formula:-

NH CNHR With a haloacid of formula:-

Hal-C-COOH The thiones of formula:-

Where Y is sulphur may be obtained from the thiones of formula:

o I l by treating the latter with phosphorus pentasulphide. If desired the thiones of formula:

Where Y is hydrocarbylimino, before the treatment with phosphorus pentasulphide.

The compounds of this invention or compositions as hereinafter defined may be used to combat a variety of insectiand other invertebratepests including the following:

Telranychus lelarius Aphis fizbae Aedes aegypti Megoura viciae Pieris brassicae Plulella mnculipennis Phaedrm cochleariae Calandra granaria Tribolium confilsum Musca domexlica Blanella germanicu Agriulimax relic'ulatus Meloidogyne incognito (red spider mite) (black aphid) (mosquito) (green aphid) (white butterfly larva) (diamond back moth larva) (mustard beetle) (grain beetle) (flour beetle) (housefly) (cockroach) (grey field slug) (nematodes) A particularly useful feature of the activity of the invention compounds is their ability to act as systemic pesticides, that is to say, their ability to move through aplant to combat infestations thereon at a site remote from the site of application of the compound.

The compounds and compositions of this invention may also be used to control a variety of plant pathogens including the following fungal diseases of plants:

(rust on wheat) (late blight on tomato) (downy mildew on vine) (powdery mildew on apple) (powdery mildew on vine) (blast on rice) (grey mould on vine) Puccinia recundila Phylophlhora in feslans Plasmopara viticula Podosphaera Ieucotriclia Uncinula necator Piricularia oryzae Bolryris cinerea wherein Q is oxygen or sulphur, or the sulphoxide or sulphone group; R, R and R, which may be the same or different, are hydrogen, or unsubstituted, or substituted, hydrocarbyl or heterocyclic radicals; and either (i) X is a group of formula:

where R and R which may be the same or different, are hydrogen, or unsubstituted or substituted, hydrocarbyl radicals, or the acyl residues of carboxylic or sulphur-containing acids; and Y is oxygen, sulphur, or the hydrocarbylimino radical; or (ii) Y is a group of formulaz where R and R, which may be the same or different, are hydrogen, or unsubstituted or substituted, hydrocarbyl radicals, or the acyl residues of carboxylic or-sulphur-containing acids; and X is oxygen, sulphur, or the hydrocarbylimino radical.

In a preferred aspect the invention provides a pesticidal composition comprising as an active ingredient a compound of formula:-

C 0-. N-li-o-N R R1 wherein R and R, which may be the same or different are hydrogen or alkyl; R is hydrogen, alkyl, alkenyl, alkylthioalkyl, alkyl-substituted amino, aralkyl, estersubstituted alkyl, or a halo-substituted nitrogencontaining aromatic monocyclic heterocycle; and R and R which may be the same or different, are hydrogen, alkyl, phenyl, halo-substituted phenyl, acyl, haloalkyl, or alkylthioalkyl. y

In an even more preferred aspect the invention provides a pesticidal composition comprising as an active ingredient a compound of formula:

Wherein R is alkyl containing up to four carbon atoms; R and R are hydrogen or alkyl containing up to four carbon atoms; R is hydrogen or methyl; and R is methyl.

In an especially preferred aspect the invention provides a pesticidal composition comprising as an active ingredient the compound having the formula:

o cirpra-li-o-N The compositions maybe used for agricultural or horticultural purposes and the type of composition used in any instance will-depend upon the particular purpose for which it is to be used.

The compositions may be in the form of dusting powders wherein the active ingredient is mixed with a solid diluent or carrier. Suitable solid diluents or carriers may be, for example, kaolin, bentonite, kieselguhr, dolomite, calcium carbonate, talc, powdered magnesium, Fullers' earth, gypsum, Hewitts earth, diatomaceious earth and china clay.

The compositions may also be in the form of liquid preparations to be used as dips or sprays which are generally aqueous dispersion of emulsions containing the active ingredient in the presence of one or more wetting agents, dispersing agents, emulsifying agents or suspending agents.

Wetting agents, dispersing agents and emulsifying agents may be of the cationic, anion or non-ionic type. Suitable agents of the cationic type include, for example quaternary ammonium compounds, for example, cetyltrimethylammonium bromine. Suitable agents of the anionic type include, for example, soaps, salts of aliphatic mono-esters of sulphuric acid, for example sodium lauryl sulphate, salts of sulphonated aromatic compounds, for example sodium dodecylbenzenesulphonate, sodium, calcium or ammonium lignosulphonate, butylnaphthalene sulphonate, and a mixture of the sodium salts of diisopropyland triisopropylnaphthalene sulphonic acids. Suitable agents of the non-ionic type include, for example, the condensation products of ethylene oxide with fatty alcohols such as oleyl alcohol or cetyl alcohol or with alkyl phenols such as octylphenol, nonylphenol and octylcresol. Other non-ionic agents are the partial esters derived from long chain fatty acids and hexitol anhydrides, the condensation products of the said partial esters with ethylene oxide, and the lecithins. Suitable suspending agents are, for example, hydrophilic colloids, for example polyvinylpyrrolidone and sodium carboxymethylcellulose, and the vegetable gums, for example gum acacia and gum tragacanth.

The aqueous dispersions or emulsions may be prepared by dissolving the active ingredient or ingredients in an organic solvent which may contain one or more wetting, dispersing or emulsifying agents and then adding the mixture so obtained to water which may likewise contain one or more wetting, dispersing or emulsifying agents. Suitable organic solvents are isopropyl alcohol, propylene glycol, diacetone alcohol, toluene, kerosene, methylnaphthalene, xylenes and trichloroethylene.

The compositions to be used as sprays may also be in the form of aerosols wherein the formulation is held in a container under pressure in the presence of a propellant such as fluorotrichloromethane or dichlorodifluoromethane.

By the inclusion of suitable additives for example for improving the distribution, adhesive power and resistance to rain on treated surfaces, the different compositions can be better adapted for the various uses for which they are intended.

The compositions which are to be used in the form of aqueous dispersions or emulsions are generally supplied in the form of a concentrate containing a high proportion of the active ingredient or ingredients, the said concentrates to be diluted with water before use. These concentrates are often required to withstand storage for prolonged periods and after such storage, to be capable of dilution with water in order to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment. The concentrates may contain -85% by weight of the active ingredient or ingredients.

When diluted to form aqueous preparations, such preparations may contain varying amounts of the active ingredient or ingredients depending upon the purpose for which they are to be used.

For agricultural or horticultural purposes, an aqueous preparation containing between 0,0001% and 0.1% by weight of the active ingredient or ingredients may be used.

The compositions of the present invention may, if desired, also comprise in addition to a compound of the present invention, at least one other biologically active ingredient, for example, in insecticide, or a fungicide.

Thus, for example, a composition of the present invention may comprise a compound of the present invention together with the gamma isomer of l,2,3,4,5,6- hexachlorocyclohexane.

In use, the invention compounds of compositions may be used to combat pests in a variety of ways. Thus the pests themselves, or the locus of the pests or the pest habitat may be treated to control the pests.

In a further feature therefore the invention provides a method of combating pests wherein the pests, the locus of the pests, or the habitat of the pests is treated with a compound or a composition according to the invention.

The invention also provides a method of treating plants with a compound of composition according to the invention to render them less susceptible to damage by pests, which may already be occurring (i.e. treatment to eradicate an infestation or infection) or which is expected to occur (i.e. treatment to protect the plant from an infestation or infection.

In a yet further feature, therefore, the invention provides a method of treating plants to render them less susceptible to damage by pests, which comprises treating the plants, or the seeds, corms, bulbs, tubers, rhizomes or other propagative parts of the plants, with a compound or composition according to the invention.

If desired the medium in which the plants are growing may be similarly treated with a compound or composition according to the invention.

In another feature, therefore the invention provides a method of treating a medium in which plants are growing or to be grown which comprises applying to the medium a compound or composition according to the invention.

The invention is illustrated, but not limited, by the following examples.

EXAMPLE 1 This example illustrates the preparation of 3,5,5- trimethyl thiazolidin-4-one-2-thione having the formula:

To a solution of methylamine in ethanol (33% w/v, 20

ml.) was added (40 ml.) and the mixture was cooled to OC,'whilst carbon disulphide (7.6 g) in ethanol (10 EXAMPLE 2 Compounds of formula:

R3 r Q wherein R, R and R have the meanings given in the Table below were prepared by a similar method to that illustrated in Example 1, using the appropriate reactants in each case. A physical characteristic is given for each compound.

R R R Physical Characteristic H H CH CH(CH mp. 115C H H CH m.p. 71-72C H H C 11,, viscous Oil H CH CH b.p. l()C/0.4 mm.

C H C H H mp. 106C EXAMPLE 3 This example illustrates the preparation of 5,5- dimethyl-2-imino-thiozolidin-4-one, having the formula:

A mixture of thiourea (19.0 g) and ethanol (150 ml) was refluxed until all the thiourea had dissolved. Ethyl 2-bromo-iso-butyrate (49.0 g.) was then added over minutes to the refluxing solution, after which the mixture was refluxed for 6 hours, kept at the ambient temper-ature for 18 hours and the ethanol removed by evaporation at reduced pressure. The residue was treated with water and then with aqueous sodium bicarbonate solution to adjust the pH to 7. The precipitated solid was collected by filtration, washed with water and dried to yield 5,5-dimethyl-2-iminothiazolidin-4-one, melting at 258C.

EXAMPLE 4 By a similar method to that illustrated in Example 3 the following compounds 4 were also prepared: 2- iminothiazolidin-4-one, melting at 258C; S-ethyl- 2iminothiazolidin4-one, melting at 200C; and 5-isopropy1-2-iminothiazolidin-4-one, melting at 231C.

EXAMPLE 5 This example illustrates the preparation of 2- oximino-3,5,5-trimethylthiazolidin-4-one, having the formula:

3,5,5-Trimethylthiazolidin-4-one-2-thione (62.0 g), bydroxylamine hydrochloride (75.0 g), pyridine (75.0 ml) and ethanol (750 ml) were refluxed together for 8 hours. The mixture was cooled and diluted with water. The precipitate was collected by filtration and recrystallised from a mixture of benzene and petroleum either to yield 2-oximino-3,5,5-trimethyl-thiazolidin- 4-one having a melting point of 216C.

EXAMPLE 6 By a procedure similar to that illustrated in the preceeding example compounds of formula:

wherein the values of R, R and R are those set out in the following table, were also prepared. The table also includes a melting point in degrees centigrade for each compound.

-Continued RI R2 R3 p C H H nC H 162 C H C H H 166 H3 CH3 N(CH;,) 174 H. C 11 CH 180 EXAMPLE 7 This example illustrates the preparation of 2- oximino-S,5-dimethyl-thiazolidin-4-one having the structure:

CI-I

EXAMPLE 8 By the use of a procedure similar to that illustrated in the preceeding example the following compounds were also prepared. They all conform to the formula:

and the values for R, R and R", together with a melting point in degrees Centigrade are set out in the table below.

R) R" m.p. "C

CH:, CH H 204 H CH CH(CH H 160 H C H H 143 H CH(CH H 159 an, 6 H, H 135 H CH CH; 170

EXAMPLE 9 This example illustrates the preparation of 3,5,5- trimethyl-2-methyl-carbamoyloxyiminothiazolidin- 4-one, (Compound N0. 4, Table I) having the formula:

2-Oximino-3,5,5-trimethylthiazolidin-4-one (15.0 g) was suspended in chloroform and methyl isocyanate (5.0 g) added, together with triethylamine (4 drops). After keeping for 4 hours at room temperature the solvent was evaporated at reduced pressure and the residual solid recrystallised from benzene to yield 3,5,5- trimethyl-Z-methylcarbamoyloxyiminothiazolidin- 4-one, having a melting point of 134.5C.

EXAMPLE 10 A similar procedure to that illustrated in the preceeding example was used for the preparation of the following compounds, using the appropriate intermediate oxime as follows: 3-isopropyl-2-methylcarbamoyloxyiminothiazolidin- 4-one (Compound No. 1, Table I) from 3-isopropyl-2- oximinothiazolidin-4-one; 3-methyl-2-methylcarbamoyloxyiminothiazolidin- 4-one (Compound No. 2, Table I) from 3-methyl-2- oximinothiazolidin-4-one; 3-ethyl-2-methylcarbamoyloxyiminothiazolidin-4-one (Compound No. 3, Table I) from 3-ethyl-2- oximinothiazolidin-4 one; 3-n-octyl-2-methylcarbamoyloxyiminothiazolidin- 4-one (Compound No. 5, Table I) from 3-n-octyI-2- oximinothiazolidin-4-one; 3,5-dimethyl-2-methylcarbamoyloxyiminothiazolidin 4-one (Compound No. 9, Table I) from 3,5-dimethyl-2- oximinothiazolidin-4-one; 3-dimethylamino-5,5-dimethyl-2-methylcarbamoyloxyiminothiazolidin-4-one (Compound No. 23, Table I) from 3-dimethylamino-5,5-dimethyl-2- oximinothiazolidin-4 one; and 3,5-dimethyl-3; -ethyl-2-methylcarbamoyloxyiminothiazolidin-4-one (Compound No. 32, Table I) from 3,5-dimethyl-3-ethyl-2-oximinothiazolidin-4-one.

EXAMPLE I I This example illustrates the preparation of 5,5- dimethyI-Z-methylcarbamoyloxyiminothiazolidin- 4-one (Compound No. 8, Table I) having the formula:

EXAMPLE 12 3O EXAMPLE 13 This example illustrates the preparation of 3-n-octyl- 2-dimethylcarbamoyloxyiminothiazolidin-4-one (Compound No. 6, Table I) having the formula:

2-oximino-3-n-octylthiazolidin-4-one (4.5 g) was suspended in dry benzene (150 ml) and sodium hydride (1.0g of percent dispersion in mineral oil) added in small portions at room temperature. After the initial effervescence had ceased the mixture was refluxed for 30 minutes and then cooled. Dimethylcarbamoyl chloride (2.2 g) was then added and the mixture again refluxed for 60 minutes, after which the mixture was cooled, poured into water, the benzene layer separated, washed with water, and dried over anhydrous magnesium sulphate. After filtration the filtrate was evaporated under reduced pressure and the residual solid recrystallised from petroleum ether to yield 3-n-octyl2- dimethylcarbamoyloxyiminothiazolidin-4-one having a melting point of 52C.

EXAMPLE 14 By a procedure similar to that illustrated in the preceeding example the following compounds were also prepared from the appropriate oximes:

3,5,5-trimethyl-2-dimeth ylcarbamoyloxyiminothiazolidin-4-one (Compound No. 7, Table I) from 3,3,5- trimethyl-Z-oximinothiazolidin-4-one; and 3-methyl-Z-dimethylcarbamoyloxyiminothiazolidin- 4-one (Compound No. ll, Table I) from 3-methyl-2- oximinothiazolidin-4-one.

EXAMPLE 15 This example illustrates the preparation of 3,3,5- trimethyl-2-methylcarbamoyloxyiminothiazolidin 4-one (Compound No. 4, Table l) having the formula:

Sodium hydride (0.05 g) was added to 5,5-dimethyl- 2-methylcarbamoyloxyiminothiazolidin-4-one (Compound No. 8, Table I; 0.49 g) in dimethylformamide (25 ml). Hydrogen was evolved over a period of about 5 minutes after which the mixture was gently warmed for 10 minutes. Methyl iodide (2c.c.) was added and the mixture gently warmed for a further 15 minutes, after which it was cooled, poured intowater and extracted with chloroform. The chloroform extract was washed with water and dried over anhydrous magnesium sulphate. After filtration the filtrate was evaporated at reduced pressure and the resultant oil'triturated with n'hexane to yield 3,5,5-trimethyl-2- methylcarbamoyloxyiminothiazolidin-4-one, identical with the product obtained by the method of Example 9.

EXAMPLE 16 By a procedure similar to that illustrated in the proceeding example there were prepared other invention 3-methylthiomethyl-5,5-dimethyl2- methylcarbamoyloxyiminothiazolidin-4-one (Compound No. 13, Table I) from 5,5-dimethyl-2- methylcarbamoyloxyiminotrhiazolidin-4-one (Compound No. 8, Table I and methyl chloromethyl thioether;

3-allyl-5,5-dimethyl-2-methylcarbamyloxyiminothiazolidin-4-one (Compound No. 15, Table I) from 5.5-dimethyl-2-methylcarbamoyloxyiminothiazolidin- 4-one (Compound No. 8, Table l) and allyl bromide;

3-methyl5-iso-propyl-2-methylcarbamoyloxyiminothiazolidin-4-one (Compound No. 16, Table I) from 5-iso-propyl-2-methylcarbamoyloxyiminothiazolidin- 4-one. (Compound No. 38. Table I) and methyl iodide;

4-one (Compound No. 38, Table I) and ethyl iodide;

3-methyl-5,5-diethyl-2-methylcarbamoyloxyiminothiazolidin-4-one (Compound No. 22, Table I) from S,5diethyl'2methylcarbamoyloximinothiazolidin- 4-one (Compound No. 20, Table l) and methyl iodide;

3-ethyl-5-iso-propyl-2-methylcarbamoyloxyiminothiazolidin-4-one (compound No. 24, Table I) from 5- iso-propyl-2-methylcarbamoyloxyiminothiazolidin- -"l-one (Compound No. 39, Table I) and ethyl iodide; 3-methyl-5-n-butyl-5-ethyl-2-methylcarbamoyloxyiminothiazolidin-4-one (Compound No. 26, Table I) from 5-n-butyl-5-ethyl2-methylcarbamoyloxyiminothiazolidin-4-one (Compound No. 25, Table I) and methyl iodide;

3-benzyl-5.S-dimethyl-2methylcarbamoyloxyiminothiazolidin-4-one (Compound No. 29, Table I) from 5.S-dimethyl-2-methylcarbamoyloxyiminothiazolidin- 4-one (Compound No. 8 Table I) and benzyl chloride;

methylcarbamoyloxyiminothiazolidin-4-one (Compound No. 31, Table I) from 5,5-dimethyl-2- methylcarbamoyloxyiminothiazolidin-4-one (Compound No. 8 Table I) and ethyl chloroacetate; 3( 2,5-dichloro-2,6-difluoropyrid-4-yly5,S-dimethyl-Z- methylcarbamoyloxyiminothiazolidin-4-one (Compound No. 41 Table I) from 5,5-dimethyl-2- methylcarbamoyloxyiminothiazolidin-4-one (Compound No. 8 Table I) and 3,5-dichloro-2,4,6- trifluoropyridine; and 3-pivaloylmethyl-5,5-dimethyl-2-methylcarbamoyloxyiminothiazolidin-4-one (Compound No. 42, Table I) from 5,S-dimethyl-2-methylcarbamoyloxyiminothiazolidinA-one (Compound No. 8 Table I) and chloromethyl t-butyl ketone.

EXAMPLE 17 This example illustrates the preparation 3.5.5- trimethyl-2(N-chloromethyl-N-methylcarbamoyl)ox yiminothiazolidin-4one (Compound No. 33, Table I) having the formula:

To a solution of 3,5,S-IrimethyI-Z-methylcarbamoyloxyiminothiazolidin-4-one (15.6 g) in methylene dichloride ml) paraformaldehyde (16.0 g) was added. The mixture was cooled to 0C and concentrated hydrochloric acid (specific gravity 1.19, 30 ml.) added with stirring at external cooling. Hydrogen chloride gas was passed into the mixture for one hour whilst the mixture temperature was kept at 0C.

The methylene chloride layer was separated, dried over anhydrous magnesium sulphate and evaporated to yield 3,5,5-trimethyl-2(N-chloromethyl-N- methylcarbamoyl)-oxyiminothiazolidin-4-one, melting at 142C.

EXAMPLE 18 This example illustrates the preparation of 3,5.5-

trimethyI-2(N-ethylthiomethyl-N- methylcarbamoyl)oxyiminothiazolidin-4-one pound No. 34 Table I) having the formula:

(Com- Ethane thiol (0.62 g) was added to a solution of sodium (0.23 g) in ethanol (25.0 ml) and to the stirred mixture was added a solution of 3,5,5-trimethyl-2(N- chloromethyl-N-methylcarbamoyl)oxyiminothiazolidin'4-one (2.7 g.) in ethanol (25.0 ml) at the ambient temperature. After keeping at the ambient temperature for 18 hours the volatile components were removed by evaporation under reduced pressure. The residue was treated with water (100 ml.) and extracted with chloroform (2 X 25 ml.) The extracts were combined, dried over anhydrous sulphate, and evaporated to yield a solid which was recrystallised from petroleum ether (boiling range 60-80C) to yield 3,5,5-trimethyl- 2(N-ethylthiomethyl-N-methylcarbamoyl)oxyiminothiazolidin-4-one, having a melting point of 74C.

EXAMPLE 19 (Com- 3,3,5-trimethyl-2(N-chloromethyl-N- methylcarbamoyl)oxyiminothiazolidin-4-one (2.0 g) was dissolved in methyl alcohol (50 ml.) warmed to 50C for a few minutes and then kept at the ambient temperature for 18 hours. Upon cooling to C a crystalline precipitate formed and this was collected by filtration and recrystallised from methanol to yield 3,3,5- trimethyl-2(N-methoxymethyl-N- methylcarbamoyl)oxyiminothiazolidin-4-one, melting at 116C.

EXAMPLE By a procedure similar to that illustrated in the previous example the preparation of another invention compound was effected using the appropriate reactants as follows: 3,5,5-trimethyl-2(N-ethoxymethyl-N- methylcarbamoyl)oxyiminothiazolidin-4-one (Compound No. 36, Table I) from 70 3,5,5-trimethyl-2(N-chloromethyl-N- methylcarbamoyl)oxyiminothiazolidin-4-one (Compound No. 22, Table l) and ethyl alcohol.

EXAMPLE 2l This example illustrates the preparation of 3,3,5- 2 trimethyl-2-phenylcarbamoyloxyiminothiazolidin- 4-one (Compound No. 18, Table I,) having the formula:

To a solution of 3,5,5-trimethyl-2- oximinothiazolidin-4-one (2.6 g) in chloroform (50 ml.) was added phenylisocyanate (1.8 g) and triethylamine (2 drops). The mixture was kept at the ambient temperature for 18 hours, after which the volatile components were removed by evaporation under reduced pressure and the residual solid recrystallized from diethyl ether to yield 3,5,5-trimethyl-2- phenylcarbamoyloxyiminothiazolidin-4-one, melting point at 98C.

EXAMPLE 22 By a similar procedure to that illustrated in the preceeding example the following compounds were also prepared using the appropriate reactants as follows: 3-methyl-2-phenylcarbamoyloxyiminothiazolidin- 4-one (Compound No. 28, Table I) from 3-methyl-2- 0ximinothiazolidin-4-one and phenyl isocyanate; and 3,5,5-trimethyl-2(3,4-dichlorophenyl)carbamoyloxyiminothiazolidin-4-one (Compound No. 37, Table I) from 3,5,5-trimethyl-2-oximinothiazolidin-4-one and 3,4-dichlorophenyl isocyanate.

EXAMPLE 23 This example illustrates the preparation of 3,5,5- trimethyl-2-carbamoyloxyiminothiazolidin-4-one (Compound No. 27, Table l) having the formula:

CHI NH O-l CH CH To a solution of 3,5 ,5-trimethyl-2- oximinothiazolidin-4-one (5.0 g) in chloroform (200 ml.) was added a solution of phosgene (3.0 g) in toluene (30 ml). After stirring for one hour at the ambient temperature, the mixture was cooled to 0C and gaseous ammonia passed in for 15 minutes. The solvents were removed by evaporation under reduced pressure and the residual solid recrystallised from a mixture of toluene and petroleum ether (boiling range 60-80C) to yield a solid which did not melt, but sublimed at a temperature above 300C.

EXAMPLE 24 This example illustrates the preparation of 5,5- dimethyl-2-(N-acetyl-N-methylcarbamoyl)oxyiminothiazolidin-4-one (Compound No. 14, Table I), having the formula:

l 3C\ H ;O

N- -O-N cu CH EXAMPLE 25 This example illustrates the preparation of 3,5,5- trimethylthiazolidin-Z,4-dithione having the formula:

S Cli N 5 A mixture of 3,5,5-trimethylthiazolidin-2-one-4-thione (8.7 g), phosphorus pentasulphide (6.0 g) and dioxan ml) was refluxed with stirring for 4 hours, after EXAMPLE 26 This example illustrates the preparation of 3,5,5- trimethyl-4-oximino-thiazolidin-Z-thionehaving the formula:

CH {1 3 HON A mixture of 3,5,5-trimethylthiazo1idin-2,4-dithione (6.0 g.), hydroxylamine hydrochloride (11.0 g.), pyridine (12.0 ml) and ethanol (150 ml.) and refluxed for eight hours. Ethanolwas evaporated under reduced pressure and water (200 ml.) added to the residue. The mixture was extracted with chloroform (3 X 5 ml.), the combined chloroform extracts being washed with a w/v solution of hydrochloric acid (3 X 100 ml.) and with water 100 m1.), dried over anhydrous magnesium sulphate, and evaporated under reduced pressure to yield a residual solid. This was recrystallised from petroleum ether (boiling range 80100C) to yield 3,5,5- trimethyl-4-oximinothiazolidin-2-thi0ne, having a melting point of 142C.

EXAMPLE 27 This example illustrates the preparation of 3,5,5- trimethyl-2-n-butyl-iminothiazolidin-4-on 4 having formula:

A mixture of 3,5,5-trimethylthiazolidin-4-one-2-thione (57.8 g) n-butylamine (25.0 g)) and ethanol (200 ml.) was refluxed for 8 hours, after which time the ethanol and excess n-butylamine were removed by evaporation under reduced pressure. The residual oil was distilled to yield 3,5,S-trimethyl-Z-n-butyliminothiazolidin- 4-one, boiling at 90C/0.16 mm. Hg., having n 1.5079.

EXAMPLE 28 This example illustrates the preparation of 3,5,5- trimethyl-Z-n-butyliminothiazolidin-4-thione having the formula:

S CH A mixture of 3,5 ,5-trimethyl-2-nbutyliminothiazo1idin-4-one (42.8 g) phosphorus pentasulphide (17.8 g) and dioxan (200 ml.) was refluxed for eight hours with brisk stirring after which the liquid was decanted, heated with animal charcoal (2.0 g.) for 10 minutes, filtered whilst hot, and then evaporated under reduced pressure. The residual oil was distilled to yield 3,5,5-trimethyl2-n-butyliminothiazolidin-4- thione, having a boiling point of 10l-102C/0.22 mm.Hg.

EXAMPLE 29 This example illustrates the preparation of 3,5,5- trimethyl-2-n-butylimino-4-oximinothiazolidine having the formula:

1 nc a m) A mixture of 3,5,5-trimethyl-2-n-butyliminothiazolidin-4-thione (18.6 g) hydroxylamine hydrochloride (17.5 g) pyridine (18.2 ml.) and ethanol (150 ml) was refluxed until evolution of hydrogen sulphide had ceased 16 hours). The ethanol was removed by evaporation under reduced pressure and the pH of the residual mixture adjusted to 7 with concentrated hydrochloric acid. The mixture was then extracted with chloroform, the extracts dried over anhydrous magnesium sulphate, and evaporated to yield a residual oil, which on trituration with low boiling petroleum ether gave a solid. This was recrystallised from aqueous ethanol to yield 3,5,5-trimethyl-2-n-butylimino-4- oximinothiazolidine having a melting point of 137C.

EXAMPLE 20 This example illustrates the preparation of 3,5,5- trimethyl-4-methyl-carbamoyloxyiminothiazolidin-Z- thione (Compound No. 44, Table 3) having the formula:

To a solution of 3,5,5-trimethy1-4-oximinothiazolidin-2-thione (5.7 g) in chloroform ml.) was added methyl isocyanate (2.1 g) and triethylamine (3 drops).

The mixture was kept at the ambient temperature for 6 hours, after which the volatile components were removed by evaporation at reduced pressure, and the residual solid recrystallised from toluene to yield 3,5,5- trimethyl-4-methylcarbamoyloxyiminothiazolidin-2- thione, melting at 147C.

EXAMPLE 31 This example illustrates the preparation of 3,5,5 trimethyl-2-n-butylimino-4-methylcarbamoyloxyiminothiazolidine (Compound No. 46, Table 3) having the formula:

To a solution of 3,5,5-trimethyl-2-n-buty|imino-4- oximinothiazolidine (2.6 g) in chloroform (50 ml.) was added methyl isocyanate (3.0 ml.) at the ambient temperature, and the mixture was kept at this temperature for 18 hours. Evaporation of'the volatile portion under reduced pressure yielded a viscous oil which was identified by infra-red and n.m.r. spectroscopy as 3,5,5- trimethyl-2-n-butylimino-4-methylcarbamoyloxyiminothiazolidine.

EXAMPLE 32 This example illustrates the preparation of 3.5.5- trimethyl-4-dimethylcarbamoyloxyiminothiazolidin-2- thione (Compound No. 45, Table I) having the formula:

ll cH rm-lf-o-N: 5 S OH To a mixture of 3,5,5-trimethyl-2- methylcarbamoyloxyimino-thiazolidin-4-one (4.6 g) and glacial acetic (25.0 ml.) was added, at the ambient temperature, hydrogen peroxide solution (30 volume, 3.0 ml.) after which the mixture was kept at the ambient temperature for 72 hours. The volatile components were removed by evaporation under reduced pressure and the residue washed with petroleum ether (boiling range 4060C) to yield 3,5,5-trimethyl-2-methylcarbamoyloxyiminothiazolidin-4-one l,l-dioxide having a melting point of 118C. The petroleum ether washings were evaporated to yield an oily mixture of 3 ,5 ,5 -trimethyl-2-methylcarbamoyloxyiminothiazolidin-4-one l-oxide with some of the dioxide.

EXAMPLE 34 This example illustrates the preparation of 2- oximino-3,5,S-trimethyloxazolidin-4-one having the formula:

. cit

HON

A mixture of 3,5,5-trimethyloxazolidin-4-one-2-thione (l5.0 g) hydroxylamine hydrochloride (25.0 g) pyridine (27.0 g) and ethanol (200 ml.) was refluxed for four hours, after which the volatile portion was removed by evaporation under reduced pressure. The re- 4 sidual oil was poured into water (200 ml.) and the solid which precipitated out was collected by filtration, washed with water and dried to yield 2-oximino-3,5,5- trimethyloxazolidin4-one, having a melting point of 246C.

EXAMPLE 35 This example illustrates the preparation of 3,5,5- trimethyl-2-methylcarbamoyloxyiminooxaxolidin- 4-one (Compound No. 47) having the formula:

A mixture of 2-oximino-3,5,S-trimethyloxazolidin- 4-one (5.9 g) chloroform ml) and methyl isocya- 6 nate (2.2 g) was kept in a moisture free atmosphere at the ambient temperature for 18 hours. Evaporation of the volatile portion of the mixture under reduced pressure yielded 3,5,5-trimethyl-2-methylcarbamoyloxyimino-oxazolidin-4-one, Melting at l35C.

EXAMPLE 36 host plant or a foodstuff on which the pests feed, and treating either or both the pests and the medium with the preparations.

The mortality of the pests was then assessed at pperi- 5 ods usually varying from one to three days after the The activity of a number of the compounds was treatment tested against a variety of insect and other invertebrate The results of the tests are given below in Table 4. ln pests. The compounds were used in the form ofa liquid this table the first column indicates the name of the preparation containing 0.1% by weight of the compest species. Each of the subsequent columns indicates pound except in the tests with Aedes aegypti where the the host plant or medium on which it was supported, preparations contained 0.01% by weight of the comthe number of days which were allowed to elapse after poundThe preparations were made by dissolving each the treatment before assessing the mortality of the of the compounds in a mixture of solvents consisting of pests, and the results obtained for each of the com- 4 parts by volume of acetone and 1 part by volume of pounds, numbered as in Tables 1 to 3. above. The asdiacetone alcohol. The solutions were then diluted with sessment is expressed in integers which range from O-3. water containing 0.01% by weight of a wetting agent 0 represents less than kill sold under the trade name *LlSSAPOL" NX until the 1 represents 3049 percent kill liquid preparations contained the required concentra- 2 represents 90 percent kill tion of the compound. Lissapol" is a Trade Mark. 3 represents over percent kill The test procedure adopted with regard to each pests 20 A dash in Table 4 indicates that no test was carried was basically the same and comprised supporting a out. The symbolAindicates that an antifeeding effect number of the pests on a medium which was usually a was observed.

TABLE 4 Support No. of Pest Species Medium days COMPOUND NO:

24689l0lll213151719202223 24 Telmnychus relurim French 3 O O 3 3 O 2 3 3 3 3 O 0 0 2 3 3 1 (red spider mites. adults) Bean TeIranyc/rus Ielarius French 3 0 0 O l 0 O 3 0 O 2 0 0 0 7 (red spider mites. eggs) Bean .Ap/lis fubae Broad 2 O 3 O 0 0 3 3 3 3 3 3 3 0 3 3 3 (green aphids) Bean Meguura \iceae Broad 2 0 3 0 O O 3 3 3 3 0 3 3 0 3 3 3 (black aphids) Bean Aedesuegypti Water I 3 O O 3 O 2 0 1 0 0 O 0 0 3 O 0 (mosquito larvae) Aedes aegypii Plywood l l 0 0 O 7 0 O l 0 0 O O 0 l 2 0 0 (mosquito adults) Muscadomexlit'u Milk/ 2 2 2 0 l O 3 0 0 2 O 2 2 l 0 (houseflies-contact test*) Sugar Musca dumt'xlica Plywood 2 O O O 0 l O O 0 O 0 O O O (houscfliesresidual test) Blarlella germunit'a l O 0 O 0 2 0 l O 3 0 3 3 O (cochroaches) Pieris brasxit'ue Cabbage 2 3 0 2 3 3 2 0 3- 2 3 3 O (cabbagc white caterpillars systemic A A A A A A A A A A A A test) Pieris hrasxime Cabbage 2 O O 3 0 0 0 3 3 0 O 3 0 O 3 3 O (cabbage white caterpillars) A A A A A A A (Contact test) PIurel/u muculipennis Mustard 2 O O 2 O O 0 2 O 0 0 O O 0 0 0 (diamond back moth. A A A A A A A A larvae systemic test) Plulella muculipcnnis Mustard 2 0 0 0 0 0 O O 0 0 0 0 0 0 0 (diamond back moth, A A A A larvae contact test) Plmetlun coc/ileariue Mustard 2 O 2 3 0 O 3 3 3 2 2 3 O 2 O 0 3 2 (mustard beetles residual test) Phuedon r'oclileariae Mustard 2 3 O 0 0 O 0 (mustard beetles A A systemic test) Calandru grunariu Grain 2 O O O O O 2 0 O 0 0 0 O l 0 2 0 (grain beetles) Tribolium confidant Grain 2 O 0 0 0 0 0 0 O O O 0 2 O (Flour beetles) Meloidogyne inmgnila Water 1 U U 0 2 0 3 0 0 0 O 0 3 3 3 0 0 (nematodes) Tcrranythus telarius French 3 0 0 0 3 3 0 0 0 0 l 0 2 (red spider mites, adults) Bean Tetranychus lelariux French 3 0 0 O 2 0 O 0 O (l 0 (J 0 (red spider mites. eggs) Bean Aphis fabue Broad 2 (J 0 O O 3 3 3 O 0 0 3 O 3 (green aphids) Bean Meguura riceae Broad 2 U 0 0 0 3 3 3 0 0 O 3 0 3 TABLE 4-Continued Support No. of

Pest Species Medium days CO PO (black aphids) Bean Aedes aegypli Water 1 0 0 0 3 3 O l 0 0 0 3 3 (mosquito larvae) Aedes aegypri Plywood 1 0 2 0 2 0 0 0 0 0 0 0 2 (mosquitos adults) Musca domestica Milk/ 2 2 0 l 0 2 0 0 0 2 l 0 3 (houseflies-contact test*) Sugar Musca dumeslica Plywood 2 0 0 0 0 0 0 0 0 0 (houseflies-residual test*) Blallella germanita l 0 0 O 0 3 3 2 0 0 0 0 0 3 (cochroaches) Pieris brassicae Cabbage 2 0 0 3 O 0 0 2 3 0 0 0 3 (cabbage white cater- A A A pillars systemic test) Pieris brmsicae Cabbage 2 2 3 3 O 0 2 2 (J 0 0 3 0 (cabbage white cater- A A A A A pillars contact test) Plulclla maculipennis Mustard 2 0 0 0 0 0 0 0 0 0 0 3 0 (diamond back moth, A A A larvae systemic test) Plutella maculipennia' Mustard 2 0 0 0 0 0 0 0 0 0 0 2 (diamond back moth, A A larvae, contact test) Phaedun caclzleariae Mustard 2 1 0 0 O 0 3 3 0 O O 0 l 3 (mustard beetles A A A A A A A A A residual test) Plwedun cachleariae Mustard 2 0 O 3 O 0 3 3 (mustard beetles A A A A A systemic test) Culandra granaria Grain 2 0 O 0 0 2 0 O 0 0 0 O 0 1 (grain beetles) Tribulium confitsum Grain 2 0 O 0 0 O 2 0 0 0 0 0 0 2 (flour beetles) Meloidogyne incognim Water 1 O 0 3 0 3 0 0 0 3 2 3 2 (nematodes) 1n the contact test the flies are sprayed directly; in the residual test the flies are placed on a medium that had previously been treated. in the systemic tests the preparations are applied to the soil in which the host plants are growing.

In the contact test the flies are sprayed directly; in the residual test the flies are placed on a medium that had previously been treated. In the synthetic tests the prep arations are applied to the soil in which the host plants are growing.

EXAMPLE 37 Compounds of the invention were tested for molluscicidal activity and details of the tests conducted are as follows.

A weighed sample of the compound under test was dissolved in 0.5 cc of an ethanol and acetone mixture (50:50 v/v). The solution was diluted with 0.5 cc. water and poured on to a calf feeding pellet in a glass petri dish and the pellet was air dried for 24 hours. The weight of compound used was chosen so that the dried pellet contained 4% by weight of the active ingredient. Two replicates each consisting of a plastic petri dish containing a pellet, 2 slugs, and a moistened filter paper to maintain a high relative humidity were used in each test. The dishes were left in the cold room (10C). After 6 days the kill was assessed.

The slugs used were Agriolimax reticulatus (Mull), and they had been starved for 24 hours before the commencement of the tests. The results of the test are set out in Table 5 below.

TAB LE 5 Continued The compounds of this invention were tested against a variety of foliar fungal diseases of plants. The technique employed is to spray the foliage of the undiseased plants with a solution of the test compound and also to drench the soil in which the plants are growing with another solution of the same test compound. All solutions for spraying and drenching contained 0.01% of the test compound. The plants were then infected with the diseases it was desired to control and after a period of days, depending upon the particular disease, the extent of the disease was visually assessed. The results are given in Table 6A below, wherein the extent of the disease is given in the form of a grading as follows:

Grading Percentage Amount of Disease 0 61 to 1 26 to 60 2 6 to 25 3 0 to 5 In Table 6 the disease is given in the first column, and in the second column is given the time which elapsed between infecting the plants and assessing the amount of disease.

TABLE 6 Disease and Plant Time interval Disease C ode Days Letter (Table 6A) Pm'cinia rez'omlim 7 A (Wheat) Pliymphlhom infi'slanx 3 B (tomato) Plusmopara i'ilit'ulu 7 C (vine) Uncinula nct'amr 10 D [vine) Piriculariu oryzae 7 E (nee) Pmlusphuvm Ieucmric'hu l F (apple) Bolrylix cinema 3 G (vine) TABLE 6A Compound No: Disease Code Letter A B C D E F G 2 2 l 0 3 O 3 0 4 2 3 l 0 0 0 0 6 0 0 0 3 0 9 3 l 2 3 0 l 0 l 5 0 I 3 3 0 0 0 l6 0 l 3 0 0 O 0 l7 3 3 3 3 0 t) 0 l8 0 O O 0 O O 2 20 0 3 O 3 l 2 0 21 0 2 3 0 0 O 0 22 l 3 0 0 l O 24 0 3 0 3 l 2 0 26 O 3 O 0 l 0 l 29 0 l 3 0 0 0 O 30 0 3 0 l O O 0 3l 0 O 0 0 0 2 0 32 0 3 0 l O l 0 33 l 3 0 l 0 l 3 34 l l 0 0 l l 35 2 l 0 0 0 43 l 2 O O 0 3 U 44 U 4 3 3 l O l 45 U 3 0 l O O 0 EXAMPLE 39 This example illustrates a dusting powder which may be applied directly to plants or other surfaces and comprises l% by weight of compound No. 4 of Table l and 99% by weight of talc.

EXAMPLE 4O EXAMPLE 41 5 Parts by weight of Compound No. 4 of Table I were thoroughly mixed in a suitable mixer with 95 Parts by weight of talc. There was thus obtained a dusting powder.

EXAMPLE 42 I0 Parts by weight of compound No. 4 of Table l, parts of an ethylene oxide-octylphenol condensate (LissapoF NX', Lissapol is a Trade 'Mark) and 80 parts by weight of diacetone alcohol were thoroughly mixed. There was thus obtained a concentrate which,

in mixing with water, gave an aqueous dispersion suitable for application as a spray in the control of insect pests.

EXAMPLE 43 This example illustrates a concentrated liquid formulation in the form of an emulsion. The ingredients listed below were mixed together in the stated proportions and the whole stirred until the constituents were dispersed.

"/z wt.

Compound No. 4 of Table l 20 LUBROL L(Lubrol' is a Trade Mark) 17 Calcium dodecylbenzenesulphonate 3 Ethylene dichloride 45 AROMASOL' H(Aromasol is a Trade Mark) 15 EXAMPLE 44 The ingredients listed below were ground together in the proportions stated to produce a powdered mixture readily dispersible in liquids.

Compound No. 10 of Table l 50 Dispersal T (Dispersol is a Trade Mark) 5 China Clay 45 EXAMPLE 45 Compound No. l l of Table l 50 Dispersol T 12.5 Calcium lignosulphonate v 5 Sodium dodecylhcnzenesulphonate 12.5 Sodium acetate 20 EXAMPLE 46 A composition suitable for use as a seed dressing was prepared by mixing all three of the ingredients set out below in the proportions stated.

, Compound No. 12 of Table l Mineral Oil 2 China Clay 18 

1. AN INSECTICIDAL COMPOSITION COMPRISING, AS ACTIVE INGREDIENT, AN INSECTICIDALLY EFFECTIVE AMOUNT OF A COMPOUND OF FORMULA:
 2. The composition of claim 1 wherein the compound is
 3. A method of combating ''''insects which comprises applying to said insects or theIr habitat thereof an insecticidally'''' effective amount of a compound of the formula:
 4. The method of claim 3 wherein the compound is
 5. A method of ''''combatting insects on plants which comprises applying to said plants an insecticidally effective amount of'''' a compound of the formula:
 6. The method of claim 5 wherein the compound is 